Additive for viscoelastic fluid

ABSTRACT

Composition and method for shortening the shear recovery time of cationic, zwitterionic, and amphoteric viscoelastic surfactant fluid systems by adding an effective amount of a co-gelling agent selected from triblock oligomeric compounds having hydrophilic (for example polyether) and hydrophobic (for example alkyl) portions. The co-gelling agent also increases fluid viscosity and very low co-gelling agent concentration is needed. Preferred surfactants are betaines and quaternary amines. The fluids are useful in oilfield treatments, for example fracturing and gravel packing.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application 11/033,651filed Jan. 12, 2005, which was published on Jul. 21, 2005 as publicationNo. 2005/0155762 Al, to issue on Jan. 22, 2008 as U.S. Pat. No.7,320,952.

This application claims the benefit of U.S. Provisional PatentApplication No. 60/538,025, filed on Jan. 21, 2004.

BACKGROUND OF THE INVENTION

The invention relates to co-gelling agents for viscoelastic surfactantfluid systems. More particularly it relates to selection andoptimization of co-gelling agents for fluid systems to be used overbroad ranges of salinity and temperature. Most particularly it relatesto co-gelling agents to shorten shear recovery times and increase theviscosity of VES's for use in oilfield treatment fluids.

Certain surfactants, when in aqueous solution, form viscoelastic fluids.Such surfactants are termed “viscoelastic surfactants”, or “VES's”.Other components, such as additional VES's, co-surfactants, buffers,acids, solvents, and salts, are optional or necessary and, among otherfunctions may increase the stability (especially thermal stability) orincrease the viscosity of the systems by modifying and/or stabilizingthe micelles; all the components together are called a viscoelasticsurfactant fluid system. Not to be limited by theory, but manyviscoelastic surfactant systems form long rod-like or worm-like micellesin aqueous solution. Entanglement of these micelle structures givesviscosity and elasticity to the fluid. For a fluid to have goodviscosity and elasticity under given conditions, proper micelles must beformed and proper entanglement is needed. This requires the surfactant'sstructure to satisfy certain geometric requirements and requires themicelles to have sufficient length or interconnections for adequateentanglements.

Many chemical additives are known to improve the theological behavior(greater viscosity and/or greater stability and/or greater brinetolerance and/or lower shear sensitivity and/or faster rehealing ifmicelles are disrupted, for example by shear). Such materials aretypically called co-surfactants, co-gelling agents, rheology modifiers,or rheology enhancers, etc., and typically are alcohols, organic acidssuch as carboxylic acids and sufonic acids, sulfonates, and others. Weshall use the term co-gelling agents here. Such materials often havedifferent effects, depending upon their exact composition andconcentration, relative to the exact surfactant composition (for examplehydrocarbon chain lengths of groups in the surfactant and co-surfactant)and concentration. For example, such materials may be beneficial at someconcentrations and harmful (lower viscosity, reduced stability, greatershear sensitivity, longer rehealing times) at others.

In particular, there is a need for chemical additives that are effectivefor increasing the viscosity of VES systems at a given temperature,and/or for increasing the temperature at which such VES systems maintainthe viscosities that make the fluids useful. Furthermore, many VES fluidsystems exhibit long viscosity recovery times after experiencingprolonged high shear. Slow recovery after shear negatively impacts dragreduction and proppant transport capability, which consequently leads toundesirably high treating pressures and risks of near wellborescreen-outs. To overcome the deleterious effects of slow shear recovery,higher VES concentrations may sometimes be used. There is a need foradditives that extend the conditions under which VES systems can beused, and reduce the amount of surfactant needed, which in turn reducesthe cost and improves clean-up in many uses, such as, but not limitedto, uses as oilfield treatment fluids, especially stimulation fluids,most especially hydraulic fracturing fluids. Although additives areknown that can shorten VES shear recovery times and increase viscosities(see for example U.S. patent application Ser. Nos. 10/994,664 and11/012,446, both of which are assigned to the same assignee as thepresent application and both of which are hereby incorporated in theirentirety), there is still a need for additional simple, inexpensiverheology enhancers.

SUMMARY OF THE INVENTION

One embodiment is an aqueous oilfield treatment composition containing aviscoelastic surfactant and a co-gelling agent. The co-gelling agent hasa structure selected from ABC and BAD, in which A and B are connected byan ether linkage or an ester linkage, B and C are connected by an etherlinkage or an ester linkage, A and D are connected by an ether linkageor an ester linkage, the two linkages in the co-gelling agent may be thesame or different, A and C are hydrophobic and may be the same ordifferent and may contain amine, amide, and ester groups, and B and Dare hydrophilic and may be the same or different. A and C are saturatedor unsaturated, linear or branched alkyl and may contain one or morearomatic rings; A and C are the same or different, and B and D are ionicor non-ionic and may be the same or different.

Examples of the composition of the co-gelling agent includeH(CH₂)_(x)(OCH₂CH₂)_(y)O(CH₂)_(z)H,H(CH₂)_(x)CO(OCH₂CH₂)_(y)OCO(CH₂)_(z)H,HO(CH₂CH₂O)_(x′)CO(CH₂)_(y′)CO(OCH₂CH₂)_(z′)OH, andHO(CH₂CH₂O)_(x′)(CH₂)_(y′)(OCH₂CH₂)_(z′)OH, in which y is from about 10to about 50, preferably from about 24 to about 36; y′ is from about 4 toabout 50, preferably from about 6 to about 24; x and z are from about 6to about 22, preferably from about 8 to about 16; and x′ and z′ are fromabout 1 to about 50, preferably from about 3 to about 40. The values ofx and z, and of x′ and z′, may be the same.

The concentration of the co-gelling agent is from about 0.005 to about3%, preferably from about 0.01 to about 0.05%, most preferably fromabout 0.01 to about 0.1%. The composition may contain a polynaphthalenesulfonate.

In a further embodiment, the viscoelastic surfactant contains azwitterionic surfactant that may have the formula:RCONH—(CH₂)_(a)(CH₂CH₂O)_(m)(CH₂)_(b)—N⁺(CH₃)₂—(CH₂)_(a′)(CH₂CH₂O)_(m′)(CH₂)_(b′)COO⁻in which R is an alkyl group that contains from about 17 to about 23carbon atoms which may be branched or straight chained and which may besaturated or unsaturated; a, b, a′, and b′ are each from 0 to 10 and mand m′ are each from 0 to 13, a and b are each 1 or 2 if m is not 0 and(a+b) is from 2 to 10 if m is 0; a′ and b′ are each 1 or 2 when m′ isnot 0 and (a′+b′) is from 1 to 5 if m′ is 0; (m+m′) is from 0 to 14; andCH₂CH₂O may also be OCH₂CH₂. As an example, the zwitterionic surfactanthas the betaine structure:

in which R is a hydrocarbyl group that may be branched or straightchained, aromatic, aliphatic or olefinic and has from about 14 to about26 carbon atoms and may contain an amine; n=about 2 to about 4; and p=1to about 5, and mixtures of these compounds. Examples of the betainestructure are oleylamidopropyl betaine and erucylamidopropyl betaine.The fluid may also contain a co-surfactant. An example of an aqueousoilfield treatment composition is one in which the viscoelasticsurfactant contains erucylamidopropyl betaine and the co-gelling agentcontains H(CH₂)_(x)CO(OCH₂CH₂)_(y)OCO(CH₂)_(z)H in which x=z=12 andy=32.

In yet a further embodiment, the viscoelastic surfactant contains acationic surfactant, for example a surfactant or mixture of surfactantshaving the structure:R₁N⁺(R₂)(R₃)(R₄) X⁻in which R₁ has from about 14 to about 26 carbon atoms and may bebranched or straight chained, aromatic, saturated or unsaturated, andmay comprise a carbonyl, an amide, a retroamide, an imide, a urea, or anamine; R₂, R₃, and R₄ are each independently hydrogen or a C₁ to aboutC₆ aliphatic group which may be the same or different, branched orstraight chained, saturated or unsaturated and one or more than one ofwhich may be substituted with a group that renders the R₂, R₃, and R₄group more hydrophilic; the R₂, R₃ and R₄ groups may be incorporatedinto a heterocyclic 5- or 6-member ring structure which includes thenitrogen atom; the R₂, R₃ and R₄ groups may be the same or different;R₁, R₂, R₃ and/or R₄ may contain one or more ethylene oxide and/orpropylene oxide units; and X⁻ is an anion; and mixtures of thesecompounds. As a further example, R₁ comprises from about 18 to about 22carbon atoms and may comprise a carbonyl, an amide, or an amine; R₂, R₃,and R₄ comprise from 1 to about 3 carbon atoms, and X⁻ is a halide. Asyet a further example, R₁ comprises from about 18 to about 22 carbonatoms and may comprise a carbonyl, an amide, or an amine, and R₂, R₃,and R₄ are the same as one another and comprise from 1 to about 3 carbonatoms.

In another embodiment, the cationic viscoelastic surfactant may alsocontain an amine, for example having the structure:R₁N(R₂)(R₃)in which R₁, R₂, and R₃ are as defined above. The amine may be present,for example, at a concentration of between about 0.01 and about 1percent.

In another embodiment, the viscoelastic surfactant contains an amineoxide.

In yet another embodiment, the aqueous oilfield treatment compositionmay optionally contain an acid selected from hydrochloric acid,hydrofluoric acid, formic acid, acetic acid, lactic acid, glycolic acid,sulfamic acid, malic acid, citric acid, tartaric acid, maleic acid,methylsulfamic acid, chloroacetic acid, and mixtures of these acids.

A further embodiment is a concentrate for addition to an aqueous fluidto form a viscoelastic fluid, the concentrate containing a freezingpoint depressant, less than about 60% water, a co-gelling agent asdescribed above, and a viscoelastic surfactant.

A further embodiment is a method of shortening the shear recovery timeof a viscoelastic surfactant based fluid involving a.) providing a fluidcontaining a viscoelastic surfactant and b.) mixing with the fluid aco-gelling agent in a concentration sufficient to shorten the shearrecovery time of the fluid. The co-gelling agent has a structureselected from ABC and BAD in which A and B are connected by an etherlinkage or an ester linkage, B and C are connected by an ether linkageor an ester linkage, A and D are connected by an ether linkage or anester linkage, the two linkages in the co-gelling agent may be the sameor different, A and C are hydrophobic and may be the same or differentand may contain amine, amide, and ester groups, and B and D arehydrophilic and may be the same or different.

Yet another embodiment is an oilfield treatment method involving: a)providing a fluid containing a viscoelastic surfactant and a co-gellingagent having a structure selected from ABC and BAD in which A and B areconnected by an ether linkage or an ester linkage, B and C are connectedby an ether linkage or an ester linkage, A and D are connected by anether linkage or an ester linkage, the two linkages in the co-gellingagent may be the same or different, A and C are hydrophobic and may bethe same or different and may contain amine, amide, and ester groups,and B and D are hydrophilic and may be the same or different, andinjecting the fluid down a well.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the viscosity of VES fluid systems, with and withoutco-gelling agents of the invention, as a function of temperature.

DETAILED DESCRIPTION OF THE INVENTION

When fluids are viscosified by the addition of viscoelastic surfactantsystems, the viscosity increase is believed to be due to the formationof micelles, for example worm-like micelles, which entangle to givestructure to the fluid that leads to the viscosity. In addition to theviscosity itself, an important aspect of a fluid's properties is thedegree and rate of viscosity-recovery or re-healing when the fluid issubjected to high shear and the shear is then reduced. For VES fluids,shear may disrupt the micelle structure, after which the structurereforms. Controlling the degree and rate of reassembling of the micellestructure (re-healing) is necessary to maximize performance of thesurfactant system for different applications. For example, in hydraulicfracturing it is critical for the fluid to regain viscosity as quicklyas possible after exiting the high-shear region in the tubulars andentering the low-shear environment in the hydraulic fracture. On theother hand, it is beneficial in coiled tubing cleanouts to impart aslight delay in regaining full viscosity in order to “jet” the solidsmore efficiently from the bottom of the wellbore into the annulus. Oncein the annulus the regained viscosity ensures that the solids areeffectively transported to the surface. Thus viscosity and shearrehealing rate are both important fluid theological properties.

Although viscoelastic surfactant fluid systems have been shown to haveexcellent viscoelastic properties for hydraulic fracturing applications,shear recovery time, not fluid viscosity, often dictates the minimumconcentration of surfactant required. For example, a fluid made with acertain concentration of surfactant may show adequate viscosity forfracturing at a given temperature, but the minimum usable concentrationmay be higher due to slow shear recovery with the lower concentration.An acceptable shear recovery time is considered to be about 15 seconds.A time longer than about 15 seconds will negatively impact dragreduction and proppant transport. Shortening the viscosity-recovery timemakes it possible to use VES fluid systems and/or concentrations thatwould otherwise not be suitable in many applications. In addition, whena rheology modifier also increases fluid viscosity, then less surfactantis needed to provide a given viscosity. Examples of rheology enhancersare given in U.S. patent application Ser. No. 10/994,664.

We have found that certain simple chemical additives, when included incertain viscoelastic surfactant fluid systems (such as cationic,amphoteric, and zwitterionic viscoelastic surfactant fluid systems,especially betaine zwitterionic viscoelastic surfactant fluid systems),in the proper concentrations relative to the surfactant activeingredients, a) significantly shorten the shear recovery times of thesystems, b) increase the viscosities of the VES systems at a giventemperature, and c) increase the temperatures at which such VES systemsmaintain viscosities that make the fluids useful for many purposes, suchas, but not limited to, uses as oilfield treatment fluids, especiallystimulation fluids, most especially hydraulic fracturing fluids. In manycases, the shear recovery is nearly instantaneous. We will call thesematerials “co-gelling agents” here. The co-gelling agents extend theconditions under which the VES systems can be used, and reduce theamount of surfactant needed, which in turn reduces the cost and improvesthe clean-up.

In general, the formulas of representative categories of chemicals thatserve as co-gelling agents are triblock oligomers whose structure can bewritten as ABC or BAD, where A and C are hydrophobic and may be the sameor different and may contain amine, amide, and ester groups, and can bean alkyl group (saturated or unsaturated, linear or branched, orcontaining one or more aromatic rings), and B and D are hydrophilic andmay be the same or different, and may be ionic, for example may bepolyacrylate, or non-ionic, with non-ionic being better for the betainesystems, and polyether being preferred. Shown below are four examples:H(CH₂)_(x)(OCH₂CH₂)_(y)O(CH₂)_(z)H  1H(CH₂)_(x)CO(OCH₂CH₂)_(y)OCO(CH₂)_(z)H  2HO(CH₂CH₂O)_(x′)CO(CH₂)_(y′)CO(OCH₂CH₂)_(z′)OH  3HO(CH₂CH₂O)_(x′)(CH₂)_(y′)(OCH₂CH₂)_(z′)OH,  4

In these formulas, y is from about 10 to about 50, preferably from about24 to about 36; y′ is from about 4 to about 50, preferably from about 6to about 24; x and z are from about 6 to about 22, preferably from about8 to about 16; and x′ and z′ are from about 1 to about 50, preferablyfrom about 3 to about 40. ABA systems in which x=z and x′=z′ arepreferred because such materials are generally easier to synthesize andtherefore are generally less expensive. ABA systems are demonstrated inthe examples below, but ABC, BAB, and BAD systems may be used.Furthermore, the A, B, C, and D blocks may be further substitutedprovided that the substitution does not change the hydrophobicity orhydrophilicity of the blocks so much that the co-gelling agent is noteffective. Such substitution may affect the suitable values of x, y, andz. Successful deviations from the basic formulae (for example the basicformula in which A and C are hydrophobic, and can be an alkyl chain(saturated or unsaturated, linear or branched, and may contain one ormore aromatic rings); B is hydrophilic, and can be ionic, for examplemay be polyacrylate, or non-ionic, with non-ionic being better for thebetaine systems; Y is preferably above 10, and x and z are preferablyless than 22) depends substantially on the surfactant and co-gellingagent concentrations, and the presence and concentration of othermaterials (especially salts and co-surfactants).

Suitable concentrations (in the final fluid system) are from about0.005% to about 3%, for example from about 0.01% to about 0.05%, forexample from about 0.01 to about 0.1%. These are very low concentrationsfor rheology enhancers or co-gelling agents.

The co-gelling agents of the present invention give the desired resultswith any VES system, for example those based on cationic, amphoteric,and zwitterionic viscoelastic surfactant systems. They have been foundto be particularly effective with certain zwitterionic surfactants. Ingeneral, particularly suitable zwitterionic surfactants have theformula:RCONH—(CH₂)_(a)(CH₂CH₂O)_(m)(CH₂)_(b)—N⁺(CH₃)₂—(CH₂)_(a′)(CH₂CH₂O)_(m′)(CH₂)_(b′)COO⁻in which R is an alkyl group that contains from about 17 to about 23carbon atoms which may be branched or straight chained and which may besaturated or unsaturated; a, b, a′, and b′ are each from 0 to 10 and mand m′ are each from 0 to 13; a and b are each 1 or 2 if m is not 0 and(a+b) is from 2 to 10 if m is 0; a′ and b′ are each 1 or 2 when m′ isnot 0 and (a′+b′) is from 1 to 5 if m is 0; (m+m′) is from 0 to 14; andCH₂CH₂O may also be OCH₂CH₂.

Preferred zwitterionic surfactants include betaines. Two suitableexamples of betaines are BET-O and BET-E. The surfactant in BET-O-30 isshown below; one chemical name is oleylamidopropyl betaine. It isdesignated BET-O-30 because as obtained from the supplier (Rhodia, Inc.Cranbury, N.J., U. S. A.) it is called Mirataine BET-O-30 because itcontains an oleyl acid amide group (including a C₁₇H₃₃ alkene tailgroup) and contains about 30% active surfactant; the remainder issubstantially water, sodium chloride, and propylene glycol. An analogousmaterial, BET-E-40, is also available from Rhodia and contains an erucicacid amide group (including a C₂₁H₄₁ alkene tail group) and isapproximately 40% active ingredient, with the remainder beingsubstantially water, sodium chloride, and isopropanol. VES systems, inparticular BET-E-40, optionally contain about 1% (of the as-receivedconcentrate) of a condensation product of a naphthalene sulfonic acid,for example sodium polynaphthalene sulfonate, as a rheology modifier, asdescribed in U. S. Patent Application Publication No. 2003-0134751. Thesurfactant in BET-E-40 is also shown below; one chemical name iserucylamidopropyl betaine. As-received concentrates of BET-E-40 wereused in the experiments reported below. BET surfactants, and other VES'sthat are suitable for the present Invention, are described in U.S. Pat.No. 6,258,859. According to that patent, BET surfactants makeviscoelastic gels when in the presence of certain organic acids, organicacid salts, or inorganic salts; in that patent, the inorganic salts werepresent at a weight concentration up to about 30%. Co-surfactants may beuseful in extending the brine tolerance, and to increase the gelstrength and to reduce the shear sensitivity of the VES-fluid, inparticular for BET-O-type surfactants. An example given in U.S. Pat. No.6,258,859 is sodium dodecylbenzene sulfonate (SDBS), also shown below.Other suitable co-surfactants include, for example those having theSDBS-like structure in which x=5-15; preferred co-surfactants are thosein which x=7-15. Still other suitable co-surfactants for BET-O-30 arecertain chelating agents such as trisodium hydroxyethylethylenediaminetriacetate. The co-gelling agents of the present invention may be usedwith viscoelastic surfactant fluid systems that contain such additivesas co-surfactants, organic acids, organic acid salts, and/or inorganicsalts.

Preferred embodiments of the present invention use betaines; mostpreferred embodiments use BET-E-40. Although experiments have not beenperformed, it is believed that mixtures of betaines, especiallyBET-E-40, with other surfactants are also suitable. Such mixtures arewithin the scope of embodiments of the invention.

Other betaines that are suitable include those in which the alkene sidechain (tail group) contains 17-23 carbon atoms (not counting thecarbonyl carbon atom) which may be branched or straight chained andwhich may be saturated or unsaturated, n=2-10, and p=1-5, and mixturesof these compounds. More preferred betaines are those in which thealkene side chain contains 17-21 carbon atoms (not counting the carbonylcarbon atom) which may be branched or straight chained and which may besaturated or unsaturated, n=3-5, and p=1-3, and mixtures of thesecompounds. The surfactants are used at a concentration of about 0.5 toabout 10%, preferably from about 1 to about 5%, and most preferably fromabout 1.5 to about 4.5%.

Exemplary cationic viscoelastic surfactants include the amine salts andquaternary amine salts disclosed in U.S. Pat. Nos. 5,979,557, and6,435,277 which have a common Assignee as the present application andwhich are hereby incorporated by reference.

Examples of suitable cationic viscoelastic surfactants include cationicsurfactants having the structure:R₁N⁺(R₂)(R₃)(R₄) X⁻in which R₁ has from about 14 to about 26 carbon atoms and may bebranched or straight chained, aromatic, saturated or unsaturated, andmay contain a carbonyl, an amide, a retroamide, an imide, a urea, or anamine; R₂, R₃, and R₄ are each independently hydrogen or a C₁ to aboutC₆ aliphatic group which may be the same or different, branched orstraight chained, saturated or unsaturated and one or more than one ofwhich may be substituted with a group that renders the R₂, R₃, and R₄group more hydrophilic; the R₂, R₃ and R₄ groups may be incorporatedinto a heterocyclic 5- or 6-member ring structure which includes thenitrogen atom; the R₂, R₃ and R₄ groups may be the same or different;R₁, R₂, R₃ and/or R₄ may contain one or more ethylene oxide and/orpropylene oxide units; and X⁻ is an anion. Mixtures of such compoundsare also suitable. As a further example, R₁ is from about 18 to about 22carbon atoms and may contain a carbonyl, an amide, or an amine, and R₂,R₃, and R₄ are the same as one another and contain from 1 to about 3carbon atoms.

Cationic surfactants having the structure R₁N⁺(R₂)(R₃)(R₄) X⁻ mayoptionally contain amines having the structure R₁N(R₂)(R₃). It is wellknown that commercially available cationic quaternary amine surfactantsoften contain the corresponding amines (in which R₁, R₂, and R₃ in thecationic surfactant and in the amine have the same structure). Asreceived commercially available VES surfactant concentrate formulations,for example cationic VES surfactant formulations, may also optionallycontain one or more members of the group consisting of solvents, mutualsolvents, organic acids, organic acid salts, inorganic salts, andoligomers, polymers, co-polymers, and mixtures of these members. Theymay also contain performance enhancers, such as viscosity enhancers, forexample polysulfonates, for example polysulfonic acids, as described incopending U. S. Patent Application Publication No. 2003-0134751 whichhas a common Assignee as the present application and which is herebyincorporated by reference.

Another suitable cationic VES is erucyl bis(2-hydroxyethyl) methylammonium chloride, also known as (Z)-13 docosenyl-N-N-bis(2-hydroxyethyl) methyl ammonium chloride. It is commonly obtained frommanufacturers as a mixture containing about 60 weight percent surfactantin a mixture of isopropanol, ethylene glycol, and water. Other suitableamine salts and quaternary amine salts include (either alone or incombination in accordance with the invention), erucyl trimethyl ammoniumchloride; N-methyl-N,N-bis(2-hydroxyethyl) rapeseed ammonium chloride;oleyl methyl bis(hydroxyethyl) ammonium chloride;erucylamidopropyltrimethylamine chloride, octadecyl methylbis(hydroxyethyl) ammonium bromide; octadecyl tris(hydroxyethyl)ammonium bromide; octadecyl dimethyl hydroxyethyl ammonium bromide;cetyl dimethyl hydroxyethyl ammonium bromide; cetyl methylbis(hydroxyethyl) ammonium salicylate; cetyl methyl bis(hydroxyethyl)ammonium 3,4,-dichlorobenzoate; cetyl tris(hydroxyethyl) ammoniumiodide; cosyl dimethyl hydroxyethyl ammonium bromide; cosyl methylbis(hydroxyethyl) ammonium chloride; cosyl tris(hydroxyethyl) ammoniumbromide; dicosyl dimethyl hydroxyethyl ammonium bromide; dicosyl methylbis(hydroxyethyl) ammonium chloride; dicosyl tris(hydroxyethyl) ammoniumbromide; hexadecyl ethyl bis(hydroxyethyl) ammonium chloride; hexadecylisopropyl bis(hydroxyethyl) ammonium iodide; and cetylamino, N-octadecylpyridinium chloride.

Amphoteric viscoelastic surfactants are also suitable. Exemplaryamphoteric viscoelastic surfactant systems include those described inU.S. Pat. No. 6,703,352, for example amine oxides. Mixtures ofzwitterionic surfactants and amphoteric surfactants are suitable. Anexample is a mixture of about 13% isopropanol, about 5% 1-butanol, about15% ethylene glycol monobutyl ether, about 4% sodium chloride, about 30%water, about 30% cocoamidopropyl betaine, and about 2%cocoamidopropylamine oxide.

Viscoelastic surfactant fluids, for example those used in the oilfield,may also contain agents that dissolve minerals and compounds, forexample in formations, scale, and filtercakes. Such agents may be, forexample, acids and chelating agents, for example hydrochloric acid,formic acid, acetic acid, lactic acid, glycolic acid, sulfamic acid,malic acid, citric acid, tartaric acid, maleic acid, methylsulfamicacid, chloroacetic acid, aminopolycarboxylic acids, 3-hydroxypropionicacid, polyaminopolycarboxylic acids, for example trisodiumhydroxyethylethylenediamine triacetate, and salts of these acids andmixtures of these acids and/or salts. For sandstone treatment, the fluidalso typically contains a hydrogen fluoride source. The hydrogenfluoride source may be HF itself or may be selected from ammoniumfluoride and/or ammonium bifluoride or mixtures of the two; when strongacid is present the HF source may also be one or more ofpolyvinylammonium fluoride, polyvinylpyridinium fluoride, pyridiniumfluoride, imidazolium fluoride, sodium tetrafluoroborate, ammoniumtetrafluoroborate, salts of hexafluoroantimony, TEFLON™ syntheticresinous fluorine-containing polymer, and mixtures. When theformation-dissolving agent is a strong acid, the fluid preferablycontains a corrosion inhibitor. The fluid optionally contains chelatingagents for polyvalent cations, for example especially aluminum, calciumand iron (in which case the agents are often called iron sequesteringagents) to prevent their precipitation. Some of the formation-dissolvingagents just described are such chelating agents as well. Chelatingagents are added at a concentration, for example, of about 0.05% (ofactive ingredient). When VES fluids contain strong acids, they aretypically not gelled and display low viscosity; when the pH increases asthe acid reacts with the mineral, the system gels and the viscosityincreases. Such fluids may be called viscoelastic diverting acids, orVDA's. The co-gelling agents of the present invention may be used inviscoelastic surfactant fluid systems containing acids and chelatingagents.

Preparation and use (mixing, storing, pumping, etc.) of the improved VESfluid systems containing co-gelling agents of the invention are the sameas for such fluids without the co-gelling agents. For example, the orderof mixing is not affected by including these co-gelling agents.Optionally, the co-gelling agents may be incorporated in surfactantconcentrates (provided that they do not affect component solubilities orconcentrate freezing points) so that the concentrates can be dilutedwith an aqueous fluid to make VES systems. This maintains theoperational simplicity of the VES systems. Such concentrates may containother components such as freezing point depressants; examples aremethanol, ethanol, isopropanol, ethylene glycol, and propylene glycol.As is normally the case in fluid formulation, laboratory tests should berun to ensure that the additives do not affect, and are not affected by,other components in the fluid (such as salts, for example). Inparticular, the co-gelling agents of the present invention may be usedwith other rheology modifiers. Adjusting the concentrations ofsurfactant, co-gelling agent, and other fluid components to account forthe effects of other components is within the scope of the invention.

The fluid may be used, for example in oilfield treatments. As examples,the fluid may be used as a pad fluid and/or as a carrier fluid and/or asa diverter in hydraulic fracturing, as a carrier fluid for lostcirculation control agents, as a carrier fluid for gravel packing, andas a diverter or a main fluid in acidizing and acid fracturing. Thefluids may also be used in other industries, such as pharmaceuticals,cosmetics, printing, and agriculture.

The optimal concentration of a given rheology enhancing additive of theinvention for a given choice of VES surfactant fluid system at a givenconcentration and temperature, and with given other materials present,can be determined by simple experiments. The total viscoelasticsurfactant concentration must be sufficient to form a viscoelastic gelunder conditions at which the surfactants have sufficient aggregationtendency. The appropriate amounts of surfactant and co-gelling agent arethose necessary to achieve the desired viscosity and shear recovery timeas determined by experiment. Again, tolerance for, and optimal amountsof other additives may also be determined by simple experiment. Ingeneral, the amount of surfactant (as active ingredient) is from about 1to about 10%. Commercially available surfactant concentrates may containsome materials that are themselves rheology enhancers, although they maybe present for example for concentrate freezing point depression, so theamount of surfactant and co-gelling agent used is determined for thespecific concentrate used. Mixtures of surfactants and/or mixtures ofco-gelling agents (including mixtures of more than one co-gelling agentof the invention, and mixtures of one or more co-gelling agents of theinvention with one or more other co-gelling agents) may be used.Mixtures of surfactants may include surfactants that are notviscoelastic surfactants when not part of a viscoelastic surfactantsystem. All mixtures are tested and optimized; for example, too muchtotal co-gelling agent may decrease the beneficial effects.

EXAMPLE 1

Upon addition of a co-gelling agent to a BET-E-40 VES system, a newfluid system was made that demonstrated good viscosity profiles even ata concentration of 2-3% VES. (Results with 3% BET-E-40 VES are shown inFIG. 1; experiments have not been performed, but it is believed thatlower concentrations can be used.) The as-received BET-E-40 used in theexperiments contained about 1% of a sodium polynaphthalene sulfonate(see below). The co-gelling agent used was an ABA type material offormula 2 above with x=z=12, and y=32 as an example to demonstrate theeffect. As shown in FIG. 1, this BET-E-40 system formed a good fluid ata concentration of 6%. Lowering the surfactant concentration to 3%without a co-gelling agent caused lowering of the fluid viscosity to toolow a value at some temperatures. Not shown, is that lowering thesurfactant concentration without a co-gelling agent also resulted inunacceptably long rehealing times after severe shear. When very smallamounts of the co-gelling agent were added to make a new fluidformulation, the new fluids had good viscosity profiles at a VESconcentration of 3%. Not shown is that the viscosity was suitable at aconcentration of 2% as well. Their shear recovery time was as good asthat of an otherwise identical fluid made with 6% VES and no co-gellingagent.

FIG. 1 gives the viscosity temperature profiles of a series of fluidsusing varied concentrations of this ABA co-gelling agent. The fluidswith co-gelling agent also contained about 0.12% of DAXAD 19, a highmolecular weight sodium polynaphthalene sulfonate available fromHampshire Chemical Corporation, Nashua, N.H., USA, and the fluidswithout co-gelling agent contained about 0.03% (for the 3% VES) andabout 0.06% (for the 6% VES) of DAXAD 17, a low molecular weight sodiumpolynaphthalene sulfonate available from Hampshire Chemical Corporation,Nashua, N.H., USA. The performance of the 3% VES system withoutco-gelling agent would not be acceptable for typical oilfield treatmentfluids once the temperature rose to above about 66° C., while with theaddition of 0.025%, 0.05% and 0.075% of the ABA co-gelling agent, theperformance of the 3% VES fluid was greatly improved. In addition, ifthe 3% VES system without co-gelling agent was sheared under severeconditions, it took a long time (about 1 minute) for the fluid to regainits viscoelasticity. Not shown is that sodium polynaphthalene sulfonateincreased the shear recovery times, in some cases up to more than 10minutes to recover. With the addition of 0.025% ABA chemical, the shearrecovery times were reduced to only a few seconds.

EXAMPLE 2

Table 1 below shows the shear recovery times observed when variousamounts of the ABA co-gelling agent of Example 1 was added to the VESsurfactant system of Example 1. In these experiments, approximately 200mL of already-mixed VES fluid was sheared at no less than 10,000 rpm forno less than 30 seconds and no more than 1 minute in a 1 L Waringblender. The shearing was stopped and timing was begun. The fluid waspoured back and forth between a beaker and the blender cup and the fluidrecovery was characterized by the recovery time estimated by visualobservation. The fluid recovery time was the time at which fluid“lipping” occurred. The fluid “lips” when inclining the upper beaker orcup containing the fluid does not result in fluid flow into thecontainer below, but rather the formation of a “lip”, and pulling thecontainer back to a vertical position pulls back the “lip”. Infracturing fluid practice, “lipping” is used to estimate when the fluidreaches its near-equilibrium elasticity. The fluids also containedexamples of clay control agents that would be used in oilfield treatmentfluids; (TMAC is tetramethyl ammonium chloride).

TABLE 1 Shear Recovery Time VES Daxad 19 Daxad 17 ABA TMAC KCl (sec) 6%0.06% 0.20% or 2% 12 3% 0.03% >120 3% >300 3% 0.12% 0.20% >300 3% 0.12%2% >300 3% 0.12% 0.025% 0.20% 18 3% 0.12% 0.050% 0.20% 12 3% 0.12%0.075% 0.20% 9 3% 0.12% 0.025% 2% 12 3% 0.12% 0.050% 2% 9 3% 0.12%0.075% 2% 9

The table shows that with the addition of very small amounts of an ABAtriblock oligomer, the shear recovery of a 3% VES fluid system can be asfast as or faster than the shear recovery of a 6% solution of the sameVES. Without the ABA triblock oligomer, the shear recovery of the 3%solution is at least 25 times slower than the shear recovery of the 6%VES.

The ABA co-gelling agent used in these examples is sufficientlyhydrophilic that a concentrate can readily be made by adding sufficientco-gelling agent, to the as-received BET-E-40 concentrate describedabove containing sodium polynaphthalene sulfonate, so that theconcentrate can be diluted with an aqueous fluid to make VES systemslike those of the example. This maintains the operational simplicity ofthe VES systems.

1. An aqueous oilfield treatment composition comprising a viscoelasticsurfactant and a co-gelling agent wherein the co-gelling agent has astructure selected from the group consisting ofH(CH₂)_(x)CO(OCH₂CH₂)_(y)OCO(CH₂)_(z)H,HO(CH₂CH₂O)_(x′)CO(CH₂)_(y′)CO(OCH₂CH₂)_(z′)OH, andHO(CH₂CH₂O)_(x′)(CH₂)_(y′)(OCH₂CH₂)_(z′)OH, in which y is from about 10to about 50, preferably from about 24 to about 36; y′ is from about 4 toabout 50, preferably from about 6 to about 24; x and z are from about 6to about 22, preferably from about 8 to about 16; and x′ and z′ are fromabout 1 to about 50, preferably from about 3 to about 40, and furtherwherein the concertration of the co-gelling agent is from about 0.005 toabout 0.075%.
 2. The composition of claim 1 wherein said viscoelasticsurfactant comprises a zwitterionic surfactant.
 3. The composition ofclaim 2 wherein said zwitterionic surfactant comprises a surfactant ormixture of surfactants having the formula:RCONH—(CH₂)_(a)(CH₂CH₂O)_(m)(CH₂)_(b)—N⁺(CH₃)₂—(CH₂)_(a′)(CH₂CH₂O)_(m′)(CH₂)_(b′)COO⁻wherein R is an alkyl group that contains from about 17 to about 23carbon atoms which may be branched or straight chained and which may besaturated or unsaturated; a, b, a′, and b′ are each from 0 to 10 and mand m′ are each from 0 to 13, a and b are each 1 or 2 if m is not 0 and(a+b) is from 2 to 10 if m is 0; a′ and b′ are each 1 or 2 when m′ isnot 0 and (a′+b′) is from 1 to 5 if m′ is 0; (m+m′) is from 0 to 14; andCH₂CH₂O may also be OCH₂CH₂.
 4. The composition of claim 3 wherein saidzwitterionic surfactant has the betaine structure:

wherein R is a hydrocarbyl group that may be branched or straightchained, aromatic, aliphatic or olefinic and has from about 14 to about26 carbon atoms and may contain an amine; n=about 2 to about 4; and p=1to about 5, and mixtures of these compounds.
 5. The composition of claim4 wherein said betaine is oleylamidopropyl betaine.
 6. The compositionof claim 4 wherein said fluid further contains a co-surfactant.
 7. Thecomposition of claim 6 wherein said viscoelastic surfactant comprises acationic surfactant.
 8. The composition of claim 7 wherein said cationicsurfactant comprises a surfactant or mixture of surfactants having thestructure:R₁N⁺(R₂)(R₃)(R₄) X⁻ in which R₁ has from about 14 to about 26 carbonatoms and may be branched or straight chained, aromatic, saturated orunsaturated, and may comprise a carbonyl, an amide, a retroamide, animide, a urea, or an amine; R₂, R₃, and R₄ are each independentlyhydrogen or a C₁ to about C₆ aliphatic group which may be the same ordifferent, branched or straight chained, saturated or unsaturated andone or more than one of which may be substituted with a group thatrenders the R₂, R₃, and R₄ group more hydrophilic; the R₂, R₃ and R₄groups may be incorporated into a heterocyclic 5- or 6-member ringstructure which includes the nitrogen atom; the R₂, R₃ and R₄ groups maybe the same or different; R₁, R₂, R₃ and/or R₄ may contain one or moreethylene oxide and/or propylene oxide units; and X⁻ is an anion; andmixtures of these compounds.
 9. The composition of claim 8 wherein R₁comprises from about 18 to about 22 carbon atoms and may comprise acarbonyl, an amide, or an amine; R₂, R₃, and R₄ comprise from 1 to about3 carbon atoms, and X⁻ is a halide.
 10. The composition of claim 8wherein R₁ comprises from about 18 to about 22 carbon atoms and maycomprise a carbonyl, an amide, or an amine, and R₂, R₃, and R₄ are thesame as one another and comprise from 1 to about 3 carbon atoms.
 11. Thecomposition of claim 8 wherein said viscoelastic surfactant furthercomprises an amine.
 12. The composition of claim 11 wherein said aminehas the structure:R₁N(R₂)(R₃).
 13. The composition of claim 12 wherein said amine ispresent at a concentration of between about 0.01 and about 1 percent.14. The composition of claim 1 wherein said viscoelastic surfactantcomprises an amine oxide.
 15. The composition of claim 1 furthercomprising an acid selected from the group consisting of hydrochloricacid, hydrofluoric acid, formic acid, acetic acid, lactic acid, glycolicacid, sulfamic acid, malic acid, citric acid, tartaric acid, maleicacid, methylsulfamic acid, chloroacetic acid, and mixures thereof. 16.The composition of claim 1 further comprising a polynaphthalenesulfonate.
 17. The composition of claim 1 wherein further the values ofx and z are the same.
 18. The composition of claim 1 wherein further thevalues of x′ and z′ are the same.